CN107958790A - Super lithium-ion capacitor and preparation method thereof - Google Patents
Super lithium-ion capacitor and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 239000011149 active material Substances 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 30
- 238000005520 cutting process Methods 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000006258 conductive agent Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011889 copper foil Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
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- 239000012528 membrane Substances 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 238000005538 encapsulation Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 239000006183 anode active material Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 58
- 238000005096 rolling process Methods 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 20
- 239000002002 slurry Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- -1 polyethylene Polymers 0.000 description 15
- 239000011888 foil Substances 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 229910021385 hard carbon Inorganic materials 0.000 description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 229910021384 soft carbon Inorganic materials 0.000 description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
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- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical group S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Abstract
本发明提供一种超级锂离子电容器及其制备方法，所述超级锂离子电容器包括外壳，在所述外壳内设置有正极及负极，所述正极与所述负极相对设置，隔膜设置在所述正极与所述负极之间，所述外壳内充有电解液，其中，所述正极包括正极集流体及设置在所述正极集流体上的正极活性物质层，所述负极包括负极集流体及设置在所述负极集流体上的负极活性物质层，所述正极活性物质层与所述负极活性物质层相对设置，所述正极集流体及所述负极集流体均为无孔集流体。其优点在于，制备工艺简单，正极及负极的集流体为无孔结构，不需经过特殊处理，提高了生产效率，并大大降低了成本，能量密度可达到30Wh/kg以上，循环寿命可达到10万次以上，具有很好的市场应用前景。The present invention provides a super lithium ion capacitor and a preparation method thereof. The super lithium ion capacitor includes a casing, a positive electrode and a negative electrode are arranged in the casing, the positive electrode is arranged opposite to the negative electrode, and the diaphragm is arranged on the positive electrode. Between the anode and the anode, the housing is filled with an electrolyte, wherein the anode includes a cathode current collector and a positive active material layer disposed on the anode collector, and the anode includes an anode collector and an anode active material layer disposed on the anode collector. The negative electrode active material layer on the negative electrode current collector, the positive electrode active material layer is arranged opposite to the negative electrode active material layer, and both the positive electrode current collector and the negative electrode current collector are non-porous current collectors. Its advantages are that the preparation process is simple, the current collectors of the positive and negative electrodes are non-porous, no special treatment is required, the production efficiency is improved, and the cost is greatly reduced. The energy density can reach more than 30Wh/kg, and the cycle life can reach 10 More than 10,000 times, it has a good market application prospect.
Description
技术领域technical field
本发明涉及新能源领域，尤其涉及一种超级锂离子电容器及其制备方法。The invention relates to the field of new energy, in particular to a super lithium ion capacitor and a preparation method thereof.
背景技术Background technique
随着社会的发展，人们对储能器件的能量密度和功率密度要求越来越高，常用的锂离子电池、双电层电容器等储能器件已经不能满足需求。超级锂离子电容器是一种新型绿色环保储能器件，集锂离子电池和双电层电容器优点于一身，具有功率密度大、能量密度高、循环性能好、使用寿命长、小型化等特点，在电子产品、风力发电、太阳能路灯、电动汽车等方面有着广泛的应用前景。With the development of society, people have higher and higher requirements for the energy density and power density of energy storage devices, and commonly used energy storage devices such as lithium-ion batteries and electric double-layer capacitors can no longer meet the demand. Super lithium-ion capacitor is a new type of green energy storage device, which combines the advantages of lithium-ion battery and electric double layer capacitor. It has the characteristics of high power density, high energy density, good cycle performance, long service life, and miniaturization. Electronic products, wind power generation, solar street lamps, electric vehicles, etc. have broad application prospects.
超级锂离子电容器的正极一般选用双电层电极，负极一般选用硬炭电极，通过对负极进行锂离子的预掺杂，使负极预先获得一定的储能能力，从而提高体系的能量密度。The positive electrode of the super lithium ion capacitor generally uses an electric double layer electrode, and the negative electrode generally uses a hard carbon electrode. By pre-doping the negative electrode with lithium ions, the negative electrode can obtain a certain energy storage capacity in advance, thereby increasing the energy density of the system.
目前，超级锂离子电容器的正极集流体和负极集流体均采用穿孔结构，以便对负极进行预掺杂处理，具有穿孔结构的集流体能够为超级锂离子电容器负极均匀且迅速的预掺杂锂离子提供通道，降低负极电位，提高超级锂离子电容器的能量密度和功率密度。At present, both the positive electrode current collector and the negative electrode current collector of super lithium ion capacitors adopt a perforated structure in order to pre-dope the negative electrode. The current collector with a perforated structure can uniformly and rapidly pre-dope lithium ions Provide a channel, reduce the potential of the negative electrode, and increase the energy density and power density of the super lithium ion capacitor.
但是，这种预掺杂的方法涉及到的工艺非常复杂，主要体现在掺杂时间非常长，而且对原材料需要进行特殊处理，这对生产效率提高和成本降低有相当的难度。However, the process involved in this pre-doping method is very complicated, mainly reflected in the very long doping time and the need for special treatment of raw materials, which is quite difficult to improve production efficiency and reduce costs.
因此，需要一种新型的超级锂离子电容器及其制作方法，解决上述问题。Therefore, a novel super lithium ion capacitor and a manufacturing method thereof are needed to solve the above problems.
发明内容Contents of the invention
本发明所要解决的技术问题是，提供一种制备工艺简单，且集流体不需要特殊处理的超级锂离子电容器及其制备方法。The technical problem to be solved by the present invention is to provide a super lithium ion capacitor with a simple preparation process and no special treatment for the current collector and a preparation method thereof.
为了解决上述问题，本发明提供了一种超级锂离子电容器，包括外壳，在所述外壳内设置有正极及负极，所述正极与所述负极相对设置，隔膜设置在所述正极与所述负极之间，所述外壳内充有电解液，其中，所述正极包括正极集流体及设置在所述正极集流体上的正极活性物质层，所述负极包括负极集流体及设置在所述负极集流体上的负极活性物质层，所述正极活性物质层与所述负极活性物质层相对设置，所述正极集流体及所述负极集流体均为无孔集流体。In order to solve the above problems, the present invention provides a super lithium ion capacitor, including a casing, a positive electrode and a negative electrode are arranged in the casing, the positive electrode is arranged opposite to the negative electrode, and the diaphragm is arranged between the positive electrode and the negative electrode. In between, the casing is filled with an electrolyte, wherein the positive electrode includes a positive electrode collector and a positive active material layer arranged on the positive electrode collector, and the negative electrode includes a negative electrode collector and is arranged on the negative electrode collector. The negative electrode active material layer on the fluid, the positive electrode active material layer is arranged opposite to the negative electrode active material layer, and both the positive electrode current collector and the negative electrode current collector are non-porous current collectors.
进一步，所述正极集流体为无孔的铝箔，所述负极集流体为无孔的铜箔。Further, the positive electrode current collector is a non-porous aluminum foil, and the negative electrode current collector is a non-porous copper foil.
进一步，所述正极活性物质层包括第一活性物质层及预嵌锂层，所述第一活性物质层设置在所述正极集流体表面，所述预嵌锂层设置在所述第一活性物质层表面。Further, the positive electrode active material layer includes a first active material layer and a pre-intercalated lithium layer, the first active material layer is disposed on the surface of the positive electrode current collector, and the pre-intercalated lithium layer is disposed on the first active material layer surface.
进一步，所述预嵌锂层为金属锂片。Further, the pre-intercalated lithium layer is a lithium metal sheet.
进一步，所述预嵌锂层的尺寸与所述第一活性物质层的尺寸相同。Further, the size of the pre-intercalated lithium layer is the same as that of the first active material layer.
进一步，所述正极活性物质的容量与所述负极活性物质的容量比值范围为1：1～1：4。Further, the ratio of the capacity of the positive electrode active material to the capacity of the negative electrode active material ranges from 1:1 to 1:4.
本发明还提供一种上述的超级锂离子电容器的制备方法，包括如下步骤：提供一正极集流体及一负极集流体，所述正极集流体及所述负极集流体均为无孔集流体；将第一活性物质涂覆在所述正极集流体上，形成第一活性物质层；将具有第一活性物质层的正极集流体制成正极极片；提供一预嵌锂层，将所述预嵌锂层覆盖在所述第一活性物质层表面，形成正极；将负极活性物质层涂覆在所述负极集流体上，涂覆有负极活性物质层的负极集流体制成负极；将正极、负极及隔膜制作形成电芯，并注入电解液，封装形成超级锂离子电容器单体；采用恒电流的方法对所述超级锂离子电容器单体进行充电，使所述负极获得预嵌锂源。The present invention also provides a method for preparing the above-mentioned super lithium ion capacitor, comprising the following steps: providing a positive current collector and a negative current collector, both of the positive current collector and the negative current collector are non-porous current collectors; The first active material is coated on the positive electrode current collector to form a first active material layer; the positive electrode current collector with the first active material layer is made into a positive electrode sheet; a pre-embedded lithium layer is provided, and the pre-embedded The lithium layer covers the surface of the first active material layer to form a positive electrode; the negative electrode active material layer is coated on the negative electrode current collector, and the negative electrode current collector coated with the negative electrode active material layer is made into a negative electrode; the positive electrode, the negative electrode And the diaphragm is made to form a cell, and the electrolyte is injected into it, and the super lithium ion capacitor is packaged to form a single super lithium ion capacitor; the super lithium ion capacitor single is charged by a constant current method, so that the negative electrode obtains a pre-embedded lithium source.
进一步，所述第一活性层物质包括按照预定比例混合的正极活性物质、导电剂及粘结剂。Further, the first active layer material includes a positive electrode active material, a conductive agent and a binder mixed according to a predetermined ratio.
进一步，所述预嵌锂层为金属锂片，将所述金属锂片压制在第一活性物质层表面。Further, the pre-intercalated lithium layer is a lithium metal sheet, and the lithium metal sheet is pressed on the surface of the first active material layer.
进一步，将具有第一活性物质层的正极集流体制成正极极片的步骤为，将第一活性物质涂覆在正极集流体上后，经过烘干、碾压、裁切、真空干燥的步骤制成正极极片。Further, the step of making the positive electrode current collector with the first active material layer into a positive electrode sheet is to apply the first active material on the positive electrode current collector, and then go through the steps of drying, rolling, cutting, and vacuum drying. Make a positive pole piece.
进一步，涂覆有负极活性物质层的负极集流体制成负极的步骤为，将负极活性物质涂覆在负极集流体上后，经过烘干、碾压、裁切、真空干燥的步骤制成负极。Further, the negative electrode current collector coated with the negative electrode active material layer is made into a negative electrode. After the negative electrode active material is coated on the negative electrode current collector, the negative electrode is made by drying, rolling, cutting, and vacuum drying. .
本发明的优点在于，用锂离子预掺杂方法使得负极的初始荷电状态达到30％-70％，制备工艺简单，正极及负极的集流体为无孔结构，不需要经过特殊处理，提高了生产效率，并大大降低了成本，该超级锂离子电容器的能量密度可达到30Wh/kg以上，循环寿命可达到10万次以上，具有很好的市场应用前景。The present invention has the advantages of using the lithium ion pre-doping method to make the initial state of charge of the negative electrode reach 30%-70%, the preparation process is simple, the current collectors of the positive electrode and the negative electrode are non-porous structures, no special treatment is required, and the The production efficiency is greatly reduced, and the cost is greatly reduced. The energy density of the super lithium ion capacitor can reach more than 30Wh/kg, and the cycle life can reach more than 100,000 times, which has a good market application prospect.
附图说明Description of drawings
图1是本发明超级锂离子电容器的结构示意图。Fig. 1 is a structural schematic diagram of the super lithium ion capacitor of the present invention.
具体实施方式Detailed ways
下面结合附图对本发明提供的超级锂离子电容器及其制备方法的具体实施方式做详细说明。The specific implementation of the super lithium ion capacitor provided by the present invention and its preparation method will be described in detail below in conjunction with the accompanying drawings.
图1是本发明超级锂离子电容器的结构示意图。请参见图1所示，本发明超级锂离子电容器包括外壳1，在所述外壳1内设置有正极2及负极3。所述正极2与所述负极3相对设置。隔膜4设置在所述正极2与所述负极3之间，所述隔膜包括聚乙烯微孔膜或聚丙烯微孔膜。Fig. 1 is a structural schematic diagram of the super lithium ion capacitor of the present invention. Please refer to FIG. 1 , the super lithium ion capacitor of the present invention includes a casing 1 , and a positive electrode 2 and a negative electrode 3 are arranged in the casing 1 . The positive electrode 2 is opposite to the negative electrode 3 . The separator 4 is arranged between the positive electrode 2 and the negative electrode 3, and the separator includes a polyethylene microporous membrane or a polypropylene microporous membrane.
所述正极2包括正极集流体20及设置在所述正极集流体20上的正极活性物质层21。所述正极集流体20为无孔集流体，例如无孔的铝箔。所述正极活性物质层21包括第一活性物质层211及预嵌锂层212，所述第一活性物质层211设置在所述正极集流体20表面，所述预嵌锂层212设置在所述第一活性物质层211表面。在一实施例中，所述预嵌锂层212为金属锂片。所述预嵌锂层212的尺寸与所述第一活性物质层211的尺寸相同，所述第一活性物质层211的活性材料为活性碳。The positive electrode 2 includes a positive electrode current collector 20 and a positive electrode active material layer 21 disposed on the positive electrode current collector 20 . The positive current collector 20 is a non-porous current collector, such as non-porous aluminum foil. The positive electrode active material layer 21 includes a first active material layer 211 and a pre-intercalated lithium layer 212, the first active material layer 211 is disposed on the surface of the positive electrode current collector 20, and the pre-intercalated lithium layer 212 is disposed on the the surface of the first active material layer 211 . In one embodiment, the pre-intercalated lithium layer 212 is a metal lithium sheet. The size of the pre-intercalated lithium layer 212 is the same as that of the first active material layer 211, and the active material of the first active material layer 211 is activated carbon.
所述负极3包括负极集流体30及设置在所述负极集流体30上的负极活性物质层31。所述负极集流体30为无孔集流体，例如，无孔的铜箔。所述正极活性物质层21与所述负极活性物质层31相对设置。所述负极活性物质层31的活性材料可以为硬炭和软碳中的一种或两种。所述正极2活性物质的容量与所述负极3活性物质的容量比值范围为1：1～1：4。The negative electrode 3 includes a negative electrode current collector 30 and a negative electrode active material layer 31 disposed on the negative electrode current collector 30 . The negative current collector 30 is a non-porous current collector, for example, a non-porous copper foil. The positive electrode active material layer 21 is disposed opposite to the negative electrode active material layer 31 . The active material of the negative electrode active material layer 31 may be one or both of hard carbon and soft carbon. The ratio of the capacity of the active material of the positive electrode 2 to the capacity of the active material of the negative electrode 3 ranges from 1:1 to 1:4.
所述外壳1内充有电解液。所述电解液由溶质、溶剂和添加剂组成，溶质为六氟磷酸锂、四氟硼酸锂，溶剂为环状碳酸酯和链状碳酸酯混合而成，添加剂包含成膜剂。所述环状碳酸酯包括丙烯碳酸酯、乙烯碳酸酯中的一种或两种；所述链状碳酸酯包括二甲基碳酸酯、二乙基碳酸酯和乙基甲基碳酸酯中的一种或两种。所述成膜稳定剂选自碳酸亚乙烯酯、亚硫酸乙烯酯、二氧化硫和二硫化碳的一种或几种。The casing 1 is filled with electrolyte solution. The electrolytic solution is composed of solute, solvent and additives. The solute is lithium hexafluorophosphate and lithium tetrafluoroborate, the solvent is a mixture of cyclic carbonate and chain carbonate, and the additive includes a film-forming agent. The cyclic carbonate includes one or both of propylene carbonate and ethylene carbonate; the chain carbonate includes one of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate one or two. The film-forming stabilizer is selected from one or more of vinylene carbonate, vinyl sulfite, sulfur dioxide and carbon disulfide.
本发明还提供了上述超级锂离子电容器的制备方法，具体包括如下步骤。The present invention also provides a preparation method for the above-mentioned super lithium ion capacitor, which specifically includes the following steps.
正极的制备：Preparation of positive electrode:
提供一正极集流体，所述正极集流体为无孔集流体，例如无孔的铝箔。A positive current collector is provided, and the positive current collector is a non-porous current collector, such as non-porous aluminum foil.
将第一活性物质涂覆在所述正极集流体上，形成第一活性物质层。所述第一活性物质包括按照预定比例混合的正极活性物质、导电剂及粘结剂。将各个物质混合形成浆料后涂布在正极集流体上。其中，所述正极活性物质可以为活性碳。Coating the first active material on the positive current collector to form a first active material layer. The first active material includes a positive electrode active material, a conductive agent and a binder mixed according to a predetermined ratio. The various substances are mixed to form a slurry and then coated on the positive electrode current collector. Wherein, the positive electrode active material may be activated carbon.
将具有第一活性物质层的正极集流体制成正极极片。制成正极极片的方法为将第一活性物质涂覆在正极集流体上后，经过烘干、碾压、裁切、真空干燥的步骤制成正极极片。The positive electrode current collector with the first active material layer is made into a positive electrode sheet. The method for making the positive electrode sheet is to coat the first active material on the positive electrode current collector, and then go through the steps of drying, rolling, cutting, and vacuum drying to make the positive electrode sheet.
提供一预嵌锂层，将所述预嵌锂层覆盖在所述第一活性物质层表面，形成正极。其中，在本具体实施方式中，所述预嵌锂层为金属锂片，将所述金属锂片压制在第一活性物质层表面。A pre-intercalated lithium layer is provided, and the pre-intercalated lithium layer is covered on the surface of the first active material layer to form a positive electrode. Wherein, in this specific embodiment, the pre-intercalated lithium layer is a lithium metal sheet, and the lithium metal sheet is pressed on the surface of the first active material layer.
负极的制备：Preparation of negative electrode:
提供一负极集流体，所述负极集流体为无孔集流体，例如无孔的铜箔。将负极活性物质层涂覆在所述负极集流体上，涂覆有负极活性物质层的负极集流体制成负极。其中，负极活性物质层由按照预定比例混合的负极活性物质、导电剂及粘结剂形成的浆料涂覆在负极集流体上形成，所述负极活性物质为软碳或者硬炭中的一种或两种。涂覆有负极活性物质层的负极集流体制成负极的步骤为，将负极活性物质层涂覆在负极集流体上后，经过烘干、碾压、裁切、真空干燥的步骤制成负极。A negative electrode current collector is provided, and the negative electrode current collector is a non-porous current collector, such as non-porous copper foil. A negative electrode active material layer is coated on the negative electrode current collector, and the negative electrode current collector coated with the negative electrode active material layer is made into a negative electrode. Wherein, the negative electrode active material layer is formed by coating the negative electrode current collector with the slurry formed by mixing the negative electrode active material, conductive agent and binder according to a predetermined ratio, and the negative electrode active material is one of soft carbon or hard carbon or two. The negative electrode current collector coated with the negative electrode active material layer is made into a negative electrode by coating the negative electrode active material layer on the negative electrode current collector, followed by drying, rolling, cutting, and vacuum drying to make the negative electrode.
超级锂离子电容器单体的制备：将正极、负极及隔膜制作形成电芯，并注入电解液，封装形成超级锂离子电容器单体；Preparation of super lithium-ion capacitor monomer: make positive electrode, negative electrode and diaphragm to form battery core, inject electrolyte, and package to form super lithium-ion capacitor monomer;
预嵌锂步骤：采用恒电流的方法对所述超级锂离子电容器单体进行充电，使所述负极获得预嵌锂源。所述恒电流的方法指的是采用恒定的电流对所述超级锂离子电容器单体进行充电。Step of pre-intercalating lithium: using a constant current method to charge the super lithium ion capacitor monomer, so that the negative electrode obtains a source of pre-intercalating lithium. The constant current method refers to charging the super lithium ion capacitor monomer with a constant current.
性能表征：将制作好的超级锂电容进行充放电，进行全性能测试。Performance characterization: charge and discharge the prepared super lithium capacitor, and conduct a full performance test.
本发明所述的超级锂离子电容器的制备方法，用锂离子预掺杂方法使得负极的初始荷电状态达到30％-70％，制备工艺简单，正极及负极的集流体为无孔结构，不需要经过特殊处理，提高了生产效率，并大大降低了成本，该超级锂离子电容器的能量密度可达到30Wh/kg以上，循环寿命可达到10万次以上，具有很好的市场应用前景。The preparation method of the super lithium ion capacitor according to the present invention uses the lithium ion pre-doping method to make the initial state of charge of the negative electrode reach 30%-70%. Special treatment is required to improve production efficiency and greatly reduce costs. The energy density of the super lithium ion capacitor can reach more than 30Wh/kg, and the cycle life can reach more than 100,000 times, which has a good market application prospect.
下面列举本发明超级锂离子电容器制备方法的几个实施例，以进一步说明本发明技术方案。Several examples of the preparation method of the super lithium ion capacitor of the present invention are listed below to further illustrate the technical solution of the present invention.
实施例1Example 1
正极制作：将活性碳、导电剂(乙炔黑)和粘结剂(丁苯橡胶)按照92：3：5的比例混合，调成浆料后涂布于20μm铝箔上，面密度155g/m2，经100℃鼓风干燥、碾压、裁片、24h真空干燥(110～120℃)制作成极片；在干燥房(露点温度-45℃)内将锂片用辊压机辊压至5μm，裁成与活性炭极片一样的尺寸，压制在活性碳极片表面。Positive electrode production: Mix activated carbon, conductive agent (acetylene black) and binder (styrene-butadiene rubber) in a ratio of 92:3:5, make a slurry and coat it on a 20μm aluminum foil with a surface density of 155g/ m2 , after 100°C blast drying, rolling, cutting, and 24h vacuum drying (110-120°C) to make pole pieces; in the drying room (dew point temperature -45°C), roll the lithium sheet to 5 μm with a roller press , cut into the same size as the activated carbon pole piece, and pressed on the surface of the activated carbon pole piece.
负极制作：将硬碳、导电剂(超级炭黑)和粘结剂(聚偏氟乙烯)按照88：5：7的比例混合调成浆料后涂布在16μm无孔铜箔上，面密度为20g/m2，经烘干(105～110℃)、碾压、裁片、24h真空干燥(110～120℃)制作成负极片。Negative electrode production: mix hard carbon, conductive agent (super carbon black) and binder (polyvinylidene fluoride) according to the ratio of 88:5:7 to make a slurry, and then coat it on a 16μm non-porous copper foil. It is 20g/m 2 , after drying (105-110°C), rolling, cutting into pieces, and 24h vacuum drying (110-120°C) to make negative electrode sheets.
以聚丙烯隔膜卷绕成电芯，然后注入1mol/L LiPF6的电解液，其中溶剂为乙烯碳酸酯、二甲基碳酸酯和乙基甲基碳酸酯，体积比为1：1：1，添加剂为成膜稳定剂碳酸亚乙烯酯，浓度为1.5％。The polypropylene separator is wound into a cell, and then injected with 1mol/L LiPF 6 electrolyte, in which the solvent is ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, and the volume ratio is 1:1:1. The additive is film-forming stabilizer vinylene carbonate, the concentration is 1.5%.
以10mA的电流对上述电容单体进行预充掺杂，然后对该单体进行性能测试。The above-mentioned capacitor monomer was pre-doped with a current of 10mA, and then the performance test of the monomer was performed.
实施例2Example 2
正极制作：将活性碳、导电剂(乙炔黑)和粘结剂(聚四氟乙烯)按照91：4：5的比例混合，调成浆料后涂布于20μm铝箔上，面密度170g/m2，经100℃鼓风干燥、碾压、裁片、24h真空干燥(110～120℃)制作成极片；在干燥房(露点温度-45℃)内将锂片用辊压机辊压至6μm，裁成与活性炭极片一样的尺寸，压制在活性碳极片表面。Positive electrode production: Mix activated carbon, conductive agent (acetylene black) and binder (polytetrafluoroethylene) according to the ratio of 91:4:5, make a slurry and coat it on 20μm aluminum foil, with an area density of 170g/m 2. After blast drying at 100°C, rolling, cutting, and 24h vacuum drying (110-120°C) to make pole pieces; in a drying room (dew point temperature -45°C), roll the lithium sheet to 6μm, cut into the same size as the activated carbon pole piece, pressed on the surface of the activated carbon pole piece.
负极制作：将软碳、导电剂(乙炔黑)和粘结剂(聚偏氟乙烯)按照88：5：7的比例混合调成浆料后涂布在16μm无孔铜箔上，面密度为21g/m2，经烘干(105～110℃)、碾压、裁片、24h真空干燥(110～120℃)制作成负极片。Negative electrode production: mix soft carbon, conductive agent (acetylene black) and binder (polyvinylidene fluoride) in a ratio of 88:5:7 to make a slurry, and then coat it on a 16 μm non-porous copper foil with an area density of 21g/m 2 , after drying (105-110°C), rolling, cutting into pieces, and 24h vacuum drying (110-120°C), it is made into negative electrode sheet.
以聚丙烯隔膜卷绕成电芯，然后注入1mol/L LiPF6的电解液，其中溶剂为乙烯碳酸酯、二甲基碳酸酯和乙基甲基碳酸酯，体积比为1：1：1，添加剂为成膜稳定剂二氧化硫，浓度为1.0％。The polypropylene separator is wound into a cell, and then injected with 1mol/L LiPF 6 electrolyte, in which the solvent is ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, and the volume ratio is 1:1:1. The additive is sulfur dioxide, a film-forming stabilizer, with a concentration of 1.0%.
以10mA的电流对上述电容单体进行预充掺杂，然后对该单体进行性能测试。The above-mentioned capacitor monomer was pre-doped with a current of 10mA, and then the performance test of the monomer was performed.
实施例3Example 3
正极制作：将活性碳、导电剂(超级炭黑)和粘结剂(聚四氟乙烯)按照90：4：6的比例混合，调成浆料后涂布于16μm铝箔上，面密度160g/m2，经100℃鼓风干燥、碾压、裁片、24h真空干燥(110～120℃)制作成极片；在干燥房(露点温度-45℃)内将锂片用辊压机辊压至6μm，裁成与活性炭极片一样的尺寸，压制在活性碳极片表面。Positive electrode production: Mix activated carbon, conductive agent (super carbon black) and binder (polytetrafluoroethylene) according to the ratio of 90:4:6, make a slurry and coat it on 16μm aluminum foil, with an area density of 160g/ m 2 , after 100°C blast drying, rolling, cutting, and 24h vacuum drying (110-120°C) to make pole pieces; in the drying room (dew point temperature -45°C), roll the lithium sheet with a roller press to 6 μm, cut into the same size as the activated carbon pole piece, and pressed on the surface of the activated carbon pole piece.
负极制作：将硬碳、导电剂(超级炭黑)和粘结剂(聚偏氟乙烯)按照90：2：8的比例混合调成浆料后涂布在12μm无孔铜箔上，面密度为23g/m2，经烘干(105～110℃)、碾压、裁片、24h真空干燥(110～120℃)制作成负极片。Negative electrode production: Mix hard carbon, conductive agent (super carbon black) and binder (polyvinylidene fluoride) in a ratio of 90:2:8 to make a slurry, and then coat it on a 12 μm non-porous copper foil. It is 23g/m 2 , after drying (105-110°C), rolling, cutting into pieces, and 24h vacuum drying (110-120°C) to make negative electrode sheets.
以聚乙烯隔膜叠片成电芯，然后注入1mol/L LiPF6的电解液，其中溶剂为乙烯碳酸酯和乙基甲基碳酸酯，体积比为1：1，添加剂为成膜稳定剂二硫化碳，浓度为2.0％。Polyethylene diaphragms are stacked into batteries, and then injected with 1mol/L LiPF 6 electrolyte, in which the solvents are ethylene carbonate and ethyl methyl carbonate, the volume ratio is 1:1, and the additive is carbon disulfide, a film-forming stabilizer. The concentration is 2.0%.
以10mA的电流对上述电容单体进行预充掺杂，然后对该单体进行性能测试。The above-mentioned capacitor monomer was pre-doped with a current of 10mA, and then the performance test of the monomer was performed.
实施例4Example 4
正极制作：将活性碳、导电剂(超级炭黑)和粘结剂(聚偏氟乙烯)按照90：4：6的比例混合，调成浆料后涂布于16μm铝箔上，面密度160g/m2，经100℃鼓风干燥、碾压、裁片、24h真空干燥(110～120℃)制作成极片；在干燥房(露点温度-45℃)内将锂片用辊压机辊压至7μm，裁成与活性炭极片一样的尺寸，压制在活性碳极片表面。Positive electrode production: Mix activated carbon, conductive agent (super carbon black) and binder (polyvinylidene fluoride) in a ratio of 90:4:6, make a slurry and coat it on 16μm aluminum foil, with an area density of 160g/ m 2 , after 100°C blast drying, rolling, cutting, and 24h vacuum drying (110-120°C) to make pole pieces; in the drying room (dew point temperature -45°C), roll the lithium sheet with a roller press to 7 μm, cut into the same size as the activated carbon pole piece, and pressed on the surface of the activated carbon pole piece.
负极制作：将硬碳、导电剂(超级炭黑)和粘结剂(PVDF)按照90：3：7的比例混合调成浆料后涂布在16μm无孔铜箔上，面密度为20g/m2，经烘干(105～110℃)、碾压、裁片、24h真空干燥(110～120℃)制作成负极片。Negative electrode production: Mix hard carbon, conductive agent (super carbon black) and binder (PVDF) according to the ratio of 90:3:7 to make a slurry, and then coat it on a 16μm non-porous copper foil with an area density of 20g/ m 2 , after drying (105-110°C), rolling, cutting into pieces, and 24h vacuum drying (110-120°C) to make negative electrode sheets.
以聚乙烯隔膜叠片成电芯，然后注入1.2mol/L LiBF4的电解液，其中溶剂为乙烯碳酸酯和碳酸丙烯酯，体积比为1：1，添加剂为成膜稳定剂亚硫酸乙烯酯，浓度为1.2％。Polyethylene diaphragms are laminated into batteries, and then injected with 1.2mol/L LiBF 4 electrolyte, in which the solvents are ethylene carbonate and propylene carbonate, the volume ratio is 1:1, and the additive is film-forming stabilizer vinyl sulfite , the concentration is 1.2%.
以10mA的电流对上述电容单体进行预充掺杂，然后对该单体进行性能测试。The above-mentioned capacitor monomer was pre-doped with a current of 10mA, and then the performance test of the monomer was performed.
实施例5Example 5
正极制作：将活性碳、导电剂(超级炭黑)和粘结剂(聚偏氟乙烯)按照90：5：5的比例混合，调成浆料后涂布于22μm铝箔上，面密度160g/m2，经100℃鼓风干燥、碾压、裁片、24h真空干燥(110～120℃)制作成极片；在干燥房(露点温度-45℃)内将锂片用辊压机辊压至7μm，裁成与活性炭极片一样的尺寸，压制在活性碳极片表面。Positive electrode production: Mix activated carbon, conductive agent (super carbon black) and binder (polyvinylidene fluoride) in a ratio of 90:5:5, make a slurry and coat it on 22μm aluminum foil, with an area density of 160g/ m 2 , after 100°C blast drying, rolling, cutting, and 24h vacuum drying (110-120°C) to make pole pieces; in the drying room (dew point temperature -45°C), roll the lithium sheet with a roller press to 7 μm, cut into the same size as the activated carbon pole piece, and pressed on the surface of the activated carbon pole piece.
负极制作：将软碳、导电剂(导电石墨)和粘结剂(PVDF)按照90：3：7的比例混合调成浆料后涂布在16μm无孔铜箔上，面密度为22g/m2，经烘干(105～110℃)、碾压、裁片、24h真空干燥(110～120℃)制作成负极片。Negative electrode production: mix soft carbon, conductive agent (conductive graphite) and binder (PVDF) according to the ratio of 90:3:7 to make a slurry, and then coat it on a 16μm non-porous copper foil with an area density of 22g/m 2. After drying (105-110°C), rolling, cutting, and 24h vacuum drying (110-120°C), the negative electrode sheet is made.
以聚丙烯隔膜叠片成电芯，然后注入1.2mol/L LiBF4的电解液，其中溶剂为乙烯碳酸酯和碳酸丙烯酯，体积比为1：1，添加剂为成膜稳定剂亚硫酸乙烯酯，浓度为1.2％。Polypropylene separators are laminated into batteries, and then injected with 1.2mol/L LiBF 4 electrolyte, in which the solvents are ethylene carbonate and propylene carbonate, the volume ratio is 1:1, and the additive is film-forming stabilizer vinyl sulfite , the concentration is 1.2%.
以10mA的电流对上述电容单体进行预充掺杂，然后对该单体进行性能测试。The above-mentioned capacitor monomer was pre-doped with a current of 10mA, and then the performance test of the monomer was performed.
实施例6Example 6
正极制作：将活性碳、导电剂(乙炔黑)和粘结剂(丁苯橡胶)按照92：3：5的比例混合，调成浆料后涂布于20μm铝箔上，面密度175g/m2，经100℃鼓风干燥、碾压、裁片、24h真空干燥(110～120℃)制作成极片；在干燥房(露点温度-45℃)内将锂片用辊压机辊压至6μm，裁成与活性炭极片一样的尺寸，压制在活性碳极片表面。Positive electrode production: Mix activated carbon, conductive agent (acetylene black) and binder (styrene-butadiene rubber) in a ratio of 92:3:5, make a slurry and coat it on a 20μm aluminum foil with an area density of 175g/ m2 , after 100°C blast drying, rolling, cutting, and 24h vacuum drying (110-120°C) to make pole pieces; in the drying room (dew point temperature -45°C), roll the lithium sheet to 6 μm with a roller press , cut into the same size as the activated carbon pole piece, and pressed on the surface of the activated carbon pole piece.
负极制作：将硬碳、软碳、导电剂(超级炭黑)和粘结剂(聚偏氟乙烯)按照58：30：5：7的比例混合调成浆料后涂布在12μm无孔铜箔上，面密度为:22g/m2，经烘干(105～110℃)、碾压、裁片、24h真空干燥(110～120℃)制作成负极片。Negative electrode production: Mix hard carbon, soft carbon, conductive agent (super carbon black) and binder (polyvinylidene fluoride) according to the ratio of 58:30:5:7 to make a slurry and coat it on 12μm non-porous copper On the foil, the areal density is 22g/m 2 , and it is made into a negative electrode sheet after drying (105-110°C), rolling, cutting, and 24h vacuum drying (110-120°C).
以聚乙烯隔膜卷绕成电芯，然后注入1mol/L LiPF6的电解液，其中溶剂为乙烯碳酸酯、二甲基碳酸酯和乙基甲基碳酸酯，体积比为1：1：1，添加剂为成膜稳定剂碳酸亚乙烯酯，浓度为1.2％。A polyethylene separator is wound into a cell, and then injected with 1mol/L LiPF 6 electrolyte, in which the solvent is ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, and the volume ratio is 1:1:1. The additive is film-forming stabilizer vinylene carbonate, the concentration is 1.2%.
以10mA的电流对上述电容单体进行预充掺杂，然后对该单体进行性能测试。The above-mentioned capacitor monomer was pre-doped with a current of 10mA, and then the performance test of the monomer was performed.
实施例7Example 7
正极制作：将活性碳、导电剂(乙炔黑)和粘结剂(丁苯橡胶)按照92：3：5的比例混合，调成浆料后涂布于25μm铝箔上，面密度180g/m2，经100℃鼓风干燥、碾压、裁片、24h真空干燥(110～120℃)制作成极片；在干燥房(露点温度-45℃)内将锂片用辊压机辊压至6μm，裁成与活性炭极片一样的尺寸，压制在活性碳极片表面。Positive electrode production: Mix activated carbon, conductive agent (acetylene black) and binder (styrene-butadiene rubber) in a ratio of 92:3:5, make a slurry and coat it on a 25μm aluminum foil with an area density of 180g/ m2 , after 100°C blast drying, rolling, cutting, and 24h vacuum drying (110-120°C) to make pole pieces; in the drying room (dew point temperature -45°C), roll the lithium sheet to 6 μm with a roller press , cut into the same size as the activated carbon pole piece, and pressed on the surface of the activated carbon pole piece.
负极制作：将硬碳、软碳、导电剂(超级炭黑)和粘结剂(聚偏氟乙烯)按照58：30：5：7的比例混合调成浆料后涂布在16μm无孔铜箔上，面密度为:22g/m2，经烘干(105～110℃)、碾压、裁片、24h真空干燥(110～120℃)制作成负极片。Negative electrode production: Mix hard carbon, soft carbon, conductive agent (super carbon black) and binder (polyvinylidene fluoride) according to the ratio of 58:30:5:7 to make a slurry and coat it on 16μm non-porous copper On the foil, the areal density is 22g/m 2 , and it is made into a negative electrode sheet after drying (105-110°C), rolling, cutting, and 24h vacuum drying (110-120°C).
以聚丙烯隔膜卷绕成电芯，然后注入1mol/L LiPF6的电解液，其中溶剂为二甲基碳酸酯、二乙基碳酸酯和乙基甲基碳酸酯，体积比为1：1：1，添加剂为成膜稳定剂碳酸亚乙烯酯，浓度为1.5％。The polypropylene separator is wound into a cell, and then injected with 1mol/L LiPF 6 electrolyte, in which the solvents are dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and the volume ratio is 1:1: 1. The additive is vinylene carbonate, a film-forming stabilizer, with a concentration of 1.5%.
以10mA的电流对上述电容单体进行预充掺杂，然后对该单体进行性能测试。The above-mentioned capacitor monomer was pre-doped with a current of 10mA, and then the performance test of the monomer was performed.
实施例8Example 8
正极制作：将活性碳、导电剂(超级炭黑)和粘结剂(聚四氟乙烯)按照91：4：5的比例混合，调成浆料后涂布于20μm铝箔上，面密度158g/m2，经100℃鼓风干燥、碾压、裁片、24h真空干燥(110～120℃)制作成极片；在干燥房(露点温度-45℃)内将锂片用辊压机辊压至8μm，裁成与活性炭极片一样的尺寸，压制在活性碳极片表面。Positive electrode production: Mix activated carbon, conductive agent (super carbon black) and binder (polytetrafluoroethylene) according to the ratio of 91:4:5, make a slurry and coat it on 20μm aluminum foil, with an area density of 158g/ m 2 , after 100°C blast drying, rolling, cutting, and 24h vacuum drying (110-120°C) to make pole pieces; in the drying room (dew point temperature -45°C), roll the lithium sheet with a roller press to 8 μm, cut into the same size as the activated carbon pole piece, and pressed on the surface of the activated carbon pole piece.
负极制作：将软碳、导电剂(超级碳纤维)和粘结剂(聚偏氟乙烯)按照91：2：7的比例混合调成浆料后涂布在16μm无孔铜箔上，面密度为20g/m2，经烘干(105～110℃)、碾压、裁片、24h真空干燥(110～120℃)制作成负极片。Negative electrode production: mix soft carbon, conductive agent (super carbon fiber) and binder (polyvinylidene fluoride) according to the ratio of 91:2:7 to make a slurry, and then coat it on a 16 μm non-porous copper foil, with an area density of 20g/m 2 , after drying (105-110°C), rolling, cutting into pieces, and 24h vacuum drying (110-120°C) to make negative electrode sheets.
以聚丙烯隔膜卷绕成电芯，然后注入1mol/L LiPF6的电解液，其中溶剂为乙烯碳酸酯和乙基甲基碳酸酯中，体积比为1：1，添加剂为成膜稳定剂二氧化硫，浓度为1.5％。The polypropylene separator is wound into a cell, and then injected with 1mol/L LiPF 6 electrolyte, in which the solvent is ethylene carbonate and ethyl methyl carbonate, the volume ratio is 1:1, and the additive is film-forming stabilizer sulfur dioxide , the concentration is 1.5%.
以10mA的电流对上述电容单体进行预充掺杂，然后对该单体进行性能测试。The above-mentioned capacitor monomer was pre-doped with a current of 10mA, and then the performance test of the monomer was performed.
对本发明制备的超级锂离子电容器性能进行测试，其结果如下表所示。The performance of the super lithium ion capacitor prepared by the present invention is tested, and the results are shown in the table below.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be considered Be the protection scope of the present invention.
Claims (10)
- A kind of 1. super lithium-ion capacitor, it is characterised in that including shell, cathode and anode are provided with the shell, The cathode is oppositely arranged with the anode, and membrane is arranged between the cathode and the anode, and described envelope filled have electricity Liquid is solved, wherein, the cathode includes plus plate current-collecting body and the positive electrode active material layer being arranged on the plus plate current-collecting body, described Positive electrode active material layer includes the first active material layer and pre- embedding lithium layer, and first active material layer is arranged on the cathode collection Flow surface, the pre- embedding lithium layer are arranged on the first active material layer surface, and the anode includes negative current collector and sets Put the negative electrode active material layer on the negative current collector, the positive electrode active material layer and the negative electrode active material layer phase To setting, the plus plate current-collecting body and the negative current collector are non-porous collector.
- 2. super lithium-ion capacitor according to claim 1, it is characterised in that the plus plate current-collecting body is non-porous aluminium Paper tinsel, the negative current collector are non-porous copper foil.
- 3. super lithium-ion capacitor according to claim 1, it is characterised in that the pre- embedding lithium layer is metal lithium sheet.
- 4. super lithium-ion capacitor according to claim 1, it is characterised in that the size of the pre- embedding lithium layer with it is described The size of first active material layer is identical.
- 5. super lithium-ion capacitor according to claim 1, it is characterised in that the capacity of the positive active material with The capacity ratio scope of the negative electrode active material is 1：1~1：4.
- A kind of 6. preparation method of the super lithium-ion capacitor described in Claims 1 to 5 any one, it is characterised in that bag Include following steps：A plus plate current-collecting body and a negative current collector are provided, the plus plate current-collecting body and the negative current collector are non-porous afflux Body；By the first active material coated on the plus plate current-collecting body, the first active material layer is formed；Anode pole piece is made in plus plate current-collecting body with the first active material layer；One pre- embedding lithium layer is provided, the pre- embedding lithium layer is covered in the first active material layer surface, forms cathode；Negative electrode active material layer is coated on the negative current collector, the negative pole currect collecting system coated with negative electrode active material layer Into anode；Cathode, anode and membrane are made to form battery core, and inject electrolyte, encapsulation forms super lithium-ion capacitor monomer；Charged using the method for constant current to the super lithium-ion capacitor monomer, the anode is obtained pre- embedding lithium Source.
- 7. the preparation method of super lithium-ion capacitor according to claim 6, it is characterised in that first active layer Material includes positive active material, conductive agent and the binding agent mixed according to predetermined ratio.
- 8. the preparation method of super lithium-ion capacitor according to claim 6, it is characterised in that the pre- embedding lithium layer is Metal lithium sheet, the first active material layer surface is compressed on by the metal lithium sheet.
- 9. the preparation method of super lithium-ion capacitor according to claim 6, it is characterised in that will have the first activity The step of anode pole piece is made in the plus plate current-collecting body of material layer is, after the first active material is coated on plus plate current-collecting body, warp Cross the step of drying, roll, cutting, being dried in vacuo and anode pole piece is made.
- 10. the preparation method of super lithium-ion capacitor according to claim 6, it is characterised in that live coated with anode Property material layer negative current collector the step of anode is made be, by negative electrode active material coated in after on negative current collector, to pass through Anode is made in the step of drying, roll, cutting, being dried in vacuo.
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